环境因素对正负表面活性剂体系相行为的影响

在1:1正负离子表面活性剂混合体系(十二烷基硫酸钠/辛基三甲基溴化铵 SDS-C8NM3Br; 十二烷基硫酸钠/十二烷基三甲基溴化铵,SDS-C12NM3Br)中加入短链脂肪醇 (乙醇,正丙醇,正丁醇),正负离子表面活性剂沉淀溶解,出现表面活性剂双水相.上相有液晶存在,下相有囊泡自发形成.折光率数据和电镜结果表明:上相为表面活性剂富集相,下相表面活性剂浓度较低.混合体系中,出现表面活性剂双水相所需短链脂肪醇的体积百分数,随短链脂肪醇的链长增加而降低.温度升高,出现表面活性剂双水相所需短链脂肪醇的体积百分数降低.对SDS/C8NM3Br/H2O体系的研究结果表明:超声处理,可使混合体系中沉淀向囊泡转化,与短链脂肪醇的加入后的作用类似.     

正、负离子碳氟-碳氢表面活性剂混合水溶液的表面活性

1　前言碳氟表面活性剂是目前所有表面活性剂中表面活性最高的一类 ,具有很多碳氢表面活性剂无法取代的特殊用途[1] 。但是碳氟表面活性剂由于合成困难 ,价格昂贵 ,实际应用受到限大限制。研究表明 ,通过碳氟表面活性剂与碳氢表面活性剂的复配 ,有可能减少碳氟表面活性剂的用量而保持其表面活性 [1] 。在所有表面活性剂混合体系中 ,正、负离子表面活性剂混合体系具有最强的协同效应 [2 ] 。但由于正、负离子表面活性剂混合溶液一般在很低浓度即形成沉淀 ,对碳氟表面活性剂更是如此。因此目前有关碳氟—碳氢混合表面活性剂的研究主要集中在同…     

正负离子表面活性剂与高聚物混合双水相体系的相行为及蛋白质的分配

报道了由正负离子表面活性剂与高聚物混合溶液形成的一种可用于蛋白质的分离及分析的新型双水相萃取体系.研究了正负离子表面活性剂(溴化十二烷基三乙铵/十二烷基硫酸钠)分别与葡聚糖和聚乙二醇混合双水相体系的形成规律、相行为及牛血清蛋白和溶菌酶在双水相体系中的分配.通过在高聚物分子中接上亲和配基,研究蛋白质在双水相体系中的亲和分配.结果表明,在该体系中,表面活性剂与高聚物分别富集于不同相中.升高温度及加入无机盐均可促进双水相体系的形成,不同蛋白质可分配于不同的相中.亲和配基的引入极大地增强了蛋白质分配的选择性.     

正负离子表面活性剂与两性表面活性剂的相互作用

本文研究正负离子表面活性剂与两性表面活性剂混合水溶液的表面性质, 以及两性表面活性剂对正负离子裘面活性剂溶解度的影响。结果表明: (1) 两性表面活性剂的加溶作用,有助于正负离子表面活性剂的溶解; (2) 加入两性表面活性剂的量适当, 混合溶液基本保持原正负离子表面活性剂的表面活性; (3) 正负离子表面活性剂与两性表面活性剂在表面层和胶团中分子间的相互作用比正负离子表面活性剂与非离子表面活性剂分子间的相互作用稍强HC-FC正负; 离子表面活性剂与两性表面活性剂混合体系在表面层中有可能形成双分子或多分子层结构。     

扩张流变法研究表面活性剂在界面上的聚集行为

近年发展起来的界面流变测定技术在研究界面性质方面具有许多独特之处.本文结合我们的工作,总结了近年来有关该技术在表面活性剂界面聚集行为研究中的应用,讨论了扩张频率、表面活性剂浓度及疏水链长、无机盐和温度对表面扩张流变行为的影响,同时探讨了小分子表面活性剂与高分子表面活性剂表面扩张流变行为的区别以及小分子表面活性剂在气/液界面与液/液表面的扩张流变性的差异.大量研究表明,借助于界面流变性的测定不仅可以研究发生在界面上和界面附近的微观弛豫过程,而且可以探讨界面上超分子聚集体的形成,进而为乳状液和泡沫等分散体系的稳定性提供依据.     

界面扩张流变方法研究大分子与表面活性剂的相互作用

结合本课题组的工作, 较系统地总结了近年来有关界面扩张流变技术在大分子/表面活性剂混合体系研究中的应用. 大量研究表明, 通过分析界面扩张粘弹性数据和界面弛豫过程的特征参数可以研究界面层微观性质, 从而阐明大分子/表面活性剂的相互作用机理, 这对实际生产和应用具有重要的指导意义.     

高浓度区正负离子表面活性剂混合胶团的形状与大小变化

本文研究高浓度区正、负离子表面活性混合胶团的形态及大小随浓度的变化规律。根据正、负离子表面活性剂混合体系的相行为,胶团溶液的光散射以及流变性质测量,提出了混合胶团的棒-球转变模型。认为在较高浓度,随浓度增大,混合胶团经历了一个长棒变短,短棒变为球状的转变过程。     

正、负离子表面活性剂混合胶团棒-球转变模型

提出正、负离子表面活性剂混合胶团的棒-球转变模型，认为在溶液浓度较高时，随浓度进一步增大，正、负离子表面活性剂混合胶团经历了一个长棒变短、短棒变为球状的转变过程，并通过混合胶团溶液的相行为、光散射及流变性质测定等加以证实。     

高浓度无机盐对正负离子等摩尔混合表面活性剂表面活性的影响

一般认为无机盐对等链长正负离子表面活性剂等摩尔混合体系的表面活性没有明显影响.通过测定等摩尔癸基三乙基溴化铵和癸烷磺酸钠混合体系在卤化钠(NaX,X=F^-,Cl^-,Br^-,I^-)溶液中的表面活性,发现高浓度的无机盐具有明显影响,使混合表面活性剂的临界胶束浓度(cmc)降低,水溶液的最低表面张力(γ_cmc)升高.无机盐的影响程度随NaX中X的离子半径增加而增大.可通过无机反离子对正负离子表面活性剂头基之间吸引作用的"屏蔽"及"盐析"作用对结果加以解释.     

低温非水环境中疏水缔合聚丙烯酸钠与两性离子表面活性剂的相互作用

疏水缔合聚合物和表面活性剂是构建黏弹性流体的重要物质, 二者的相互作用对流体性质具有显著影响, 一直是该领域的研究热点, 但此前的研究仅聚焦于水溶液中室温及以上温度范围, 而零下极端低温环境中的相互作用尚未涉及. 本文以疏水缔合聚丙烯酸钠(HMPA)为模型聚合物, 研究了低温(-20~20 ℃)环境中其与两性离子表面活性剂N-(顺-二十二碳-13-烯酸酰胺基丙基)-N,N-二甲基羧酸甜菜碱(EDAB)在乙二醇/水混合溶剂中的相互作用及混合体系的流变性质. 先后考察了HMPA溶解于纯水和乙二醇/水混合溶剂时的流变行为和HMPA-EDAB在乙二醇/水混合溶剂中的流变行为及自组装结构形貌. 研究发现, 加入50%(体积分数)的乙二醇会阻碍HMPA疏水支链形成缔合结构, 减弱其增黏性能, 但同时也会大幅降低体系的冰点. 在HMPA- EDAB混合体系中, HMPA疏水支链会进入EDAB胶束内核自组装形成混合胶束. 混合胶束的形貌取决于 HMPA和EDAB的浓度及环境温度, 进而影响体系的流变行为. 零下的低温有助于EDAB形成蠕虫状胶束, 因此HMPA与EDAB表现出更强的协同增效作用.     

Molecular dynamics study of catanionic bilayers composed of ion pair amphiphile with double-tailed cationic surfactant

The physical stability of catanionic vesicles is important for the development of novel drug or DNA carriers. For investigating the mechanism by which catanionic vesicles are stabilized, molecular dynamics (MD) simulation is an attractive approach that provides microscopic structural information on the vesicular bilayer. In this study, MD simulation was applied to investigate the bilayer properties of catanionic vesicles composed of an ion pair amphiphile (IPA), hexadecyltrimethylammonium-dodecylsulfate (HTMA-DS), and a double-tailed cationic surfactant, ditetradecyldimethylammonium chloride (DTDAC). Structural information regarding membrane elasticity and the organization and conformation of surfactant molecules was obtained based on the resulting trajectory. Simulation results showed that a proper amount of DTDAC could be used to complement the asymmetric structure between HTMA and DS, resulting in an ordered hydrocarbon chain packing within the rigid membrane observed in the mixed HTMA-DS/DTDAC system. The coexistence of gel and fluid phases was also observed in the presence of excess DTDAC. MD simulation results agreed well with results obtained from experimental studies examining mixed HTMA-DS/DTDAB vesicles.     

Bile salt-induced vesicle-to-micelle transition in catanionic surfactant systems: steric and electrostatic interactions

The vesicle-to-micelle transition (VMT) was realized in catanionic surfactant systems by the addition of two kinds of bile salts, sodium cholate (SC) and sodium deoxycholate (SDC). It was found that steric interaction between the bile salt and catanionic surfactant plays an important role in catanionic surfactant systems that are usually thought to be dominated by electrostatic interaction. The facial amphiphilic structure and large occupied area of the bile salt are crucial to the enlargement of the average surfactant headgroup area and result in the VMT. Moreover, bile salts can also induce a macroscopic phase transition. Freeze-fracture transmission electron microscopy, dynamic light scattering, isothermal titration calorimetry, and absorbance measurements were used to follow the VMT process.     

Catanionic aggregates formed from drugs and lauric or capric acids enable prolonged release from gels

The aim of this study was to add to the range of charged surfactants that can be used to form catanionic aggregates with oppositely charged surface active drug substances; and to apply these aggregates to prolong drug release from gels. The surfactants used in this study, lauric and capric acids are of natural origin-unlike traditionally used, synthetic, surfactants. The mixtures of drug substances and oppositely charged surfactants were studied visually and with cryogenic transmission electron microscopy. Drug release from gels was studied with a modified USP paddle method. This study shows that lauric and capric acids are as, or even more, active in forming catanionic aggregates than traditionally used surfactants such as sodium dodecyl sulfate. It is shown that the length of the hydrophobic part of the surfactant plays an important role in the formation of pharmaceutically interesting catanionic aggregates. As seen in previous studies, using catanionic vesicles prolongs the drug release from gels and decreases the apparent diffusion coefficient by a factor of 10-50, compared to a gel containing only drug substance.     

Cytotoxicity characterization of catanionic vesicles in RAW 264.7 murine macrophage-like cells

In comparison with cationic liposomes, catanionic vesicles possess more attractive properties such as stability and lower cost, and these characteristics may make them suitable as a non-viral vehicle and for other biomedical applications such as vaccine adjuvants. However, very little is known about their possible cytotoxic mechanisms in cellular system. Also, this information is vital for the future development of safe biomedical systems. In the current study, the cytotoxic effect of catanionic vesicles, consisting of anionic surfactant (SDS), cationic surfactant (HTMAB), and cholesterol, in cultured RAW 264.7 murine macrophage-like cells was determined. The treatment of catanionic vesicles produced a dose-dependent effect on macrophage cells. RAW 264.7 cells exposed to catanionic vesicles exhibited morphological features of apoptosis such as chromatin condensation. Typical apoptotic ladders were observed in DNA extracted from RAW 264.7 cells treated by catanionic vesicles. Analysis from flow cytometry demonstrated an increase of hypodiploid DNA population (sub-G1) and a simultaneous decrease of diploid DNA content, indicating that DNA cleavage occurred after exposure of the cells with catanionic vesicles. In addition, it was shown that pretreatment of RAW 264.7 cells with the general caspase inhibitor (zVAD-fmk) did not prevent apoptosis induced by catanionic vesicles, suggesting that apoptosis in macrophage cells followed a caspase-independent pathway induced by catanionic vesicles. These data provide novel insight into the effect of catanionic vesicles on the mechanisms of cell death induced by catanionic vesicles.     

The pH-Dependent Surface Activity of a Hydrocarbon/Fluorocarbon Catanionic Surfactant for Water/Hydrofluoroether Microemulsions: The Characterization of a New Acid/Soap Complex

The pH sensitivity of a hydrocarbon/fluorocarbon catanionic surfactant is investigated. The catanionic surfactant is sensitive to low pH, which results in the precipitation of an acid/soap complex. This complex is identified by IR, NMR and confirmed by x-ray crystallography.     

Temperature-controlled vesicle aggregation in the mixed system of sodium n-dodecyl sulfate/n-dodecyltributylammonium bromide

Temperature-controlled vesicle aggregation was investigated in a catanionic surfactant system of sodium n-dodecyl sulfate/n-dodecyltributylammonium bromide. Vesicle aggregation took place as the temperature reached the critical value (Tc). Tc can be adjusted by the variations of the total surfactant concentration and the mixed molar ratio. It was also found that the temperature variation above Tc can greatly influence the vesicle aggregation rate. The vesicle aggregation process was irreversible as long as T >/= Tc, whereas the vesicle disaggregation process occurred only below Tc.     

Phase behavior in mixtures of cationic and anionic surfactants in aqueous solutions

Phase behavior of cationic/anionic surfactant mixtures of the same chain length (n=10, 12 or 14) strongly depends on the molar ratio and actual concentration of the surfactants. Precipitation of catanionic surfactant and mixed micelles formation are observed over the concentration range investigated. Coacervate and liquid crystals are found to coexist in the transition region from crystalline catanionic surfactant to mixed micelles.The addition of oppositely charged surfactant diminishes the surface charge density at the mixed micelle/solution interface and enhances the apparent degree of counterion dissociation from mixed micelles. Cationic surfactants have a greater tendency to be incorporated in mixed micelles than anionic ones.     

Synthesis of Poly(3,4-ethylenedioxythiophene) Hollow Spheres in CTAB/DBS — Mixed Surfactant Solutions

Summary: Hollow microspheres of PEDOT (poly(3,4-ethylenedioxythiophene) ranging from 0.5 to 10 µm have been synthesized by chemically oxidative polymerization of EDOT(3,4-ethylenedioxythiophene) using ammonium persulfate in a catanionic surfactant solution obtained by mixing cetyltrimethylammonium bromide (CTAB) and sodium dodecylbenzenesulfonate (SDBS). The effect of the molar ratio of CTAB to SDBS on the morphology of the PEDOT oxidation products has been investigated using SEM and TEM and by an analysis of the structural properties using UV-visible, FTIR and Raman spectroscopies, elemental analysis and conductivity measurements. The electro-catalytic activity of PEDOT hollow microspheres for the oxidation of ascorbic acid was investigated by cyclic voltammetry in a pH 6 citrate/phosphate buffer solution and compared to the activity of granular PEDOT particles formed in the absence of the catanionic surfactant.     

甲酰胺与正负离子表面活性剂有序溶液的研究

对羧酸钠与烷基三甲基溴化铵1：1混合体系的研究表明：常温下各体系在不同比例甲酰胺（FA）／水混合溶剂中，表面张力随浓度变化均有明显的转折点，显示了混合体系中胶团的存在．实验中发现随混合溶剂中FA比例增加，各体系的临界胶团浓度（cmc）增大．在较高温度下发现在甲酰胺中亦存在着因胶团形成而产生的表面张力-浓度对数（γ－logc）曲线的转折点，利用相分离模型对体系胶团热力学参数进行了计算．并探讨了FA对正负离子表面活性剂囊泡的影响．     

Stabilization of catanionic vesicles via polymerization

Polymerizable cationic surfactant methacryloyloxyoctyl trimethylammonium bromide (MOTB) and anionic surfactant sodium 4-(omega-methacryloyloxyoctyl)oxy benzene sulfonate (MOBS) were synthesized. Stable catanionic vesicles can spontaneously form upon mixing the two oppositely charged surfactants in aqueous solution, which was further permanently fixed by polymerization. Surface tensiometry, nuclear magnetic resonance (NMR), static and dynamic laser light scattering (LLS), and cryogenic transmission electron microscopy (cryo-TEM) were used in combination to characterize the catanionic vesicles before and after polymerization. The kinetics of formation and breakdown of unpolymerized catanionic vesicles were studied in detail employing stopped-flow light scattering. In contrast to unpolymerized vesicles, the polymerized ones exhibit permanent stability under external perturbations such as dilution or adding excess MOTB. A tentative explanation is proposed about why free radical polymerization can successfully fix the catanionic vesicles, the structure of which is well-known to be in dynamic equilibrium exchange with unimers.